FABRICATION, CHARACTERIZATION, AND IRRADIATION OF AN AUSTENITIC OXIDE DISPERSION STRENGTHENED STEEL SUITED FOR NEXT GENERATION NUCLEAR APPLICATIONS

As nuclear energy systems become more advanced, the materials encompassing them need to perform at higher temperatures for longer periods of time. In this Master’s thesis we experiment with an oxide dispersion strengthened (ODS) austenitic steel that has been recently developed. ODS materials have a small concentration of nano oxide particles dispersed in their matrix, and typically have higher strength and better extreme temperature creep resistance characteristics than ordinary steels. However, no ODS materials have ever been installed in a commercial power reactor to date. Being a newer research material, there are many unanswered phenomena that need to be addressed regarding the performance under irradiation. Furthermore, due to the ODS material traditionally needing to follow a powder metallurgy fabrication route, there are many processing parameters that need to be optimized before achieving a nuclear grade material specification. In this Master’s thesis we explore the development of a novel ODS processing technology conducted in Beijing, China, to produce solutionized bulk ODS samples with ~97% theoretical density. This is done using relatively low temperatures and ultra high pressure (UHP) equipment, to compact the mechanically alloyed (MA) steel powder into bulk samples without any thermal phase change influence or oxide precipitation. By having solutionized bulk ODS samples, transmission electron microscopy (TEM) observation of nano oxide precipitation within the steel material can be studied by applying post heat treatments. These types of samples will be very useful to the science and engineering community, to answer questions regarding material powder compacting, oxide synthesis, and performance. Subsequent analysis performed at Queen’s University included X-ray diffraction (XRD) and inductively coupled plasma optical emission spectrometry (ICP-OES). Additional TEM in-situ 1MeV Kr2+ irradiation experiments coupled with energy dispersive X-ray (EDX) techniques, were also performed on large (200nm+) non-stoichiometric oxides embedded within the austenite steel grains, in an attempt to quantify the elemental compositional changes during high temperature (520oC) heavy ion irradiation.

Studies on the ignition behaviour of boron powder

The ignition behaviour of boron powder, prepared through electrowinning process, was studied by using thermogravimetry coupled with simultaneous differential thermal analysis (TG-SDTA). The dependence of the inception of the ignition reaction on the partial pressure of oxygen, particle size of the boron powder and heating rate was investigated. It was observed that all these factors affect the ignition temperature. Boron powder with a mean particle size of about 10 mu m was found to be susceptible to ignition in oxygen even at 783K. In general, the susceptibility to ignition was found to vary inversely with the degree of crystallinity. Presence of carbon was found to retard the oxidation of boron and raise the ignition temperature. These results are useful in safe handling and storage of finely divided boron powder and in the subsequent production of boron carbide from it. (C) 2009 Elsevier B.V. All rights reserved.

Kinetics of oxidation of boron powder

The kinetics of the oxidation of electrodeposited boron powder and the boron powder produced by the reduction process were studied using thermogravimetry (TG). The oxidation was carried out by heating boron powder in a stream of oxygen. Both isothermal and non-isothermal methods were used to study the kinetics. Model-free isoconversional method was used to derive the kinetics parameters. A two step oxidation reaction (exothermic) was observed. The oxidation reaction could not be completed due to the formation of glassy layer of boric oxide on the surface of boron powder which acts as a barrier for further diffusion of oxygen into the particle. The activation energy obtained using model-free method for electrodeposited boron is 122 +/- 7 kJ mol(-1) whereas a value of 205 +/- 9 kJ mol(-1) was obtained for boron produced by the reduction process (commercially procured boron). Mechanistic interpretation of the oxidation reaction was done using model based method. The activation energy was found to depend on the size distribution of the particles and specific surface area of the powder. (C) 2010 Elsevier B.V. All rights reserved.

Reactive hot pressing of Ti-B-C and Ti-C at 1200 degrees C

Stoichiometric and non-stoichiometric powder mixtures of Ti-B4C and Ti-C with 1 wt% Ni were reactively hot pressed at 40 MPa, 1200 degrees C for 30 min. In both systems, the combined presence of Ni and non-stoichiometry enabled complete densification. While in Ti-C, non-stoichiometry by itself plays a significant role in promoting densification, the formation of intermediate borides in Ti-B4C powder mixtures requires the additional presence of Ni which promotes full reaction through the formation of a transient liquid as established previously in Ti-BN powder mixtures.

Processing of enriched elemental boron (B-10 similar to 65 at. %)

Procedures were developed for purification and processing of electrodeposited enriched boron powder for control rod application in India's first commercial Proto Type Fast Breeder Reactor (PFBR). Methodology for removal of anionic (F-, Cl-, BF4-) and cationic (Fe2+, Fe3+, Ni2+) impurities was developed. Parameters for grinding boron flakes obtained after electrodeposition were optimized to obtain the boron powder having particle size less than 100 gm. The rate of removal of impurities was studied with respect to time and concentration of the reagents used for purification. Process parameters for grinding and removal of impurities were optimized. A flowsheet was proposed which helps in minimizing the purification time and concentration of the reagent used for the effective removal of impurities. The purification methodology developed in this work could produce boron that meets the technical specifications for control rod application in a fast reactor.

A synchrotron powder X-ray diffraction study of the skutterudite-related phases AB1.5Te1.5 (A=Co, Rh, Ir; B= Ge, Sn)

X-ray resonant scattering has been exploited to investigate the crystal structure of the AB1.5Te1.5 phases (A = Co, Rh, Ir; B = Ge, Sn). Analysis of the diffraction data reveals that CoGe1.5Te1.5 and ASn1.5Te1.5 adopt a rhombohedral skutterudite-related structure, containing diamond-shape B2Te2 rings, in which the B and Te atoms are ordered and trans to each other. Anion ordering is however incomplete, and with increasing the size of both cations and anions, the degree of anion ordering decreases. By contrast, the diffraction data of IrGe1.5Te1.5 are consistent with an almost statistical distribution of the anions over the available sites, although some ordered domains may be present. The thermoelectric properties of these materials are discussed in the light of these results.

Effect of microstructure on the mechanical behavior of b-modified ti-6al-4v alloys

Small additions of B to Titanium alloys refine the as-cast microstructure significantly and hence improve their mechanical performance. In this work, tensile, fracture and fatigue properties of the as-cast and HIPed Ti-6Al-4V alloy with hypoeutectic wt.% of B additions have been examined, with particular emphasis on identifying the microstructural length scale that controls the mechanical properties of these alloys.

Structure of the noncubic phase in the ferroelectric state of Pr-substituted SrTiO3

Sr1−xPrxTiO3 has recently been shown to exhibit ferroelectricity at room temperature. In this paper powder x-ray and neutron-diffraction patterns of this system at room temperature have been analyzed to show that the system exhibits cubic (Pm-3m) structure for x<=0.05 and tetragonal (I4/mcm) for x>0.05. The redundancy of the noncentrosymmetric structural model (I4cm) in the ferroelectric state suggests the absence of long-range ordered ferroelectric domains and supports the relaxor ferroelectric model for this system.

Competing A-site and B-site driven ferroelectric instabilities in the (1-x)PbTiO3-(x)BiAlO3 system

The system (1-x)PbTiO3-(x)BiAlO3 has been investigated with regard to its solid solubility, crystal structure, microstructure, and ferroelectric transition. The unit cell volume and the tetragonality exhibit anomalous behavior near x=0.10. The Curie point (T-C) of PbTiO3 was however found to be nearly unchanged. The study seems to suggest that the decrease in the stability of the ferroelectric state due to dilution of the Ti-sublattice by smaller sized Al+3 ions is compensated by the increase in the ferroelectric stability by the Bi+3 ions.

Micromechanisms of damage in a hypereutectic Ti-6Al-4V-B alloy

The tensile stress–strain response and fracture in a hypereutectic Ti–6Al–4V–1.7B (weight percent) alloy were investigated by employing interrupted tensile tests combined with acoustic emission measurements, with the aim to identify the cause for the observed low ductility in this alloy. These tests were complemented with microscopy. The alloy contains TiB whiskers of different length scales, the majority of which include micro-whiskers ( 5–10 μm length) and a few primary-whiskers ( 200–300 μm length). Although the fracture of both types of whiskers occur during deformation, the former leads to a gradual decrease in the secant modulus whereas initiation of the latter leads to a drastic drop in the modulus along with failure of the specimen, limiting the ductility.

Elastic modulus of Ti-6Al-4V-xB alloys with B up to 0.55 wt.%

An anomalous variation in the experimental elastic modulus, E, of Ti-6Al-4V-xB (with x up to 0.55 wt.%) is reported. Volume fractions and moduli of the constituent phases were measured using microscopy and nanoindentation,respectively. These were used in simple micromechanical models to examine if the E values could be rationalized. Experimental E values higher than the upper bound estimates suggest complex interplay between microstructural modifications, induced by the addition of B, and properties.

Diffusion Studies in A(3)B Compounds with A15 Structure

There is a constant effort to understand the defect structure and diffusion behavior in intermetallic compounds with the A15 structure. Diffusion of elements in intermetallic compounds depends mainly on antisites and vacancies on different sublattices. In this article, we shall discuss the diffusion of elements in A(3)B compounds with the A15 structure.

Unconventional mechanism of stabilization of a tetragonal phase in the perovskite ferroelectric (PbTiO3)(1-x)(BiFeO3)(x)

Temperature-dependent x-ray powder-diffraction study of the tetragonal compositions of PbTiO3-BiFeO3 series has revealed that, unlike for all the known ferroelectric perovskites, the compositions exhibiting giant tetragonality is stabilized from the cubic phase via a complex transition pathway which involve (i) formation of minor monoclinic phase with a large pseudotetragonality along with an intermediate tetragonal phase (major) with a small tetragonality, (ii) gradual vanishing of the intermediate tetragonal phase and concomitant increase in the monoclinic regions, and finally (iii) gradual transformation of the monoclinic phase to the tetragonal phase with giant tetragonality.The system seems to adopt such a complex transition pathway to create amicrostructure with very large number of domains and interfaces for stress relief, which would not have been possible in case of a direct cubic-tetragonal transition.